CN109503912B - Particle-reinforced rubber material capable of being repeatedly processed and preparation method thereof - Google Patents
Particle-reinforced rubber material capable of being repeatedly processed and preparation method thereof Download PDFInfo
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- CN109503912B CN109503912B CN201811299776.2A CN201811299776A CN109503912B CN 109503912 B CN109503912 B CN 109503912B CN 201811299776 A CN201811299776 A CN 201811299776A CN 109503912 B CN109503912 B CN 109503912B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/164—Aluminum halide, e.g. aluminium chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/168—Zinc halides
Abstract
The invention discloses a particle-reinforced rubber material capable of being repeatedly processed and a preparation method thereof. According to the invention, metal chloride is added into epoxy rubber filled with silicate particles as a catalyst, and interfacial silicon ether bond is generated by the addition reaction of a rubber matrix epoxy group and a silanol group on the surface of a silicate filler under the action of hot pressing, so that the crosslinking and the reinforcement of a rubber material are realized. The rearrangement of the topological structure of the cross-linked network of the rubber material is realized by utilizing the alkoxy exchange reaction among the silyl ether cross-linked bonds at high temperature, so that the cross-linked rubber material can be repeatedly processed. According to the invention, the crosslinking and repeated processing of the silicate particle filled epoxy rubber material are realized based on the silicon ether exchange reaction, the rubber material has high physical and mechanical properties, can be repeatedly processed, and has high reprocessing performance retention rate. The method has simple process equipment, wide raw material variety and low price, is suitable for the commonly used silicate particle filled epoxy rubber material in industry, and has important application prospect in the aspect of recycling the rubber material.
Description
Technical Field
The invention relates to the field of rubber recovery, in particular to a particle-reinforced rubber material capable of being repeatedly processed and a preparation method thereof. The method utilizes the silicon ether exchange reaction to prepare the epoxy rubber material which can be processed and crosslinked by silicate particles.
Background
The rubber has unique high elasticity and has irreplaceable effect in various fields of national economy, national defense and the like. However, rubber raw rubber needs to be compounded with nanoparticles to obtain reinforcement, and the interfacial action of rubber and nanoparticles is a key factor for determining the dispersion of nanoparticles and the performance of rubber materials. The construction of rubber-nanoparticle interfacial bonding by utilizing reactive groups between rubber molecular chains and fillers is an effective method for improving interfacial interaction. Meanwhile, the rubber material is a typical thermosetting material, the recycling of the rubber material is very difficult due to the covalent bond crosslinking property of the rubber material, and the accumulation of a large amount of rubber material wastes not only causes resource waste, but also causes serious environmental problems. With the increasing shortage of rubber resources and the gradual improvement of environmental awareness in recent years, the reprocessing and recycling of the crosslinked rubber materials are receiving wide attention.
The construction of a covalent self-adaptive cross-linking network in a molecular network of a polymer matrix can endow a thermosetting polymer material with reworkable characteristics, and is one of the key research directions of recycling of the thermosetting material at present. By covalently adaptive cross-linked networks (CANs), we mean reversible covalently cross-linked networks that have a chemical response to external stimuli such as light, heat, pH, and the like. The CANs are not different from the common covalent cross-linking network in a steady state, and have specific cross-linking network topological structure and cross-linking density. Under the action of external stimulation, the CANs can realize the recombination of network topological structures through the exchangeable reaction of cross-linked bonds, and further realize the 'remodeling' of polymer material structures. Up to now, transesterification, transalkylation, olefin metathesis, siloxane silanol exchange and disulfide exchange have been used for the preparation of reprocessable covalently crosslinked polymer materials. However, the polymer materials are all prepared by complicated monomer polymerization, part of monomers can be obtained only by complex design and synthesis, the synthesis process is complex and long-consuming, and the prepared polymer materials have low mechanical properties, so that the wide application is difficult to realize.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a particle-reinforced repeatable processing rubber material and a preparation method thereof.
The basic principle of the invention is as follows: directly adding metal chloride with Lewis acidity into an epoxy rubber material filled with silicate particles to catalyze the formation of silicon ether bonds at the rubber/particle interface to prepare a silicate particle crosslinked rubber material; based on the alkoxy exchange reaction mechanism of the silicon ether cross-linking bond, the metal chloride is utilized to catalyze the exchange reaction between the silicon ether cross-linking bonds, so that the topological structure of the rubber cross-linking network is rearranged at high temperature, and the repeatable reprocessing of the cross-linked rubber material is realized.
The purpose of the invention is realized by the following technical scheme.
The invention provides a preparation method of a particle-reinforced reworkable rubber material, which comprises the following steps:
(1) sequentially adding the epoxy rubber, the silicate filler (particles) and the catalyst into an open mill or an internal mixer for mixing to obtain rubber compound;
(2) and adding an anti-aging agent into the rubber compound at room temperature, and then carrying out hot-pressing crosslinking to obtain a silicate particle crosslinked epoxy rubber material, namely the particle reinforced repeatable processing rubber material.
Further, the repeated processing comprises the steps of crushing vulcanized rubber into rubber powder with the particle size of 80 meshes, and then hot-pressing the rubber powder into rubber, wherein the hot-pressing temperature of the rubber powder is 150-.
Further, in the step (1), the rubber content of the mixed rubber is 65.5-90.5 wt.%, the filler content in the mixed rubber is 9-33 wt.%, and the catalyst content in the mixed rubber is 0.5-1.5 wt.%.
Further, in the step (1), the epoxy rubber is one or more of epoxidized butadiene rubber, epoxidized natural rubber, epoxidized styrene-butadiene rubber, epoxidized nitrile rubber and epoxidized ethylene propylene rubber.
Further, in the step (1), the epoxy degree of the epoxy rubber is 20% -50%.
In step (1), the silicate filler is at least one selected from silica, montmorillonite, kaolin, vermiculite, rectorite, sepiolite, attapulgite, imogolite, mica and halloysite.
Further, in the step (1), the catalyst is a metal chloride, and is one or more of aluminum chloride, magnesium chloride, ferric chloride, zinc chloride, stannic chloride, stannous chloride and niobium pentachloride.
Further, in the step (1), the blending temperature is 30-80 ℃ for 10-20 minutes.
Further, in the step (2), the anti-aging agent comprises p-phenylenediamine, phenols and quinolines; is N-isopropyl-N ' -phenyl-p-phenylenediamine (age resister 4010NA), N-cyclohexyl-N ' -phenyl-p-phenylenediamine (age resister 4010), N- (1, 3-dimethyl) butyl-N ' -phenyl-p-phenylenediamine (age resister 4020), N-diphenyl-p-phenylenediamine (age resister H), pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (age resister 1010), 2 ' -methylenebis (4-methyl-6-tert-butylphenol) (age resister 2246), 2,4, 6-tri-tert-butylphenol (age resister 246), 4' -thiobis (6-tert-butyl-3-methylphenol) (age resister 100), More than one of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (antioxidant RD), 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline (antioxidant AW) and 9, 9-dimethylacridine (antioxidant BLE), wherein the amount of the antioxidant is 1.5-4 wt.% of the mass of the epoxy rubber.
Further, in the step (2), the hot-pressing crosslinking is carried out at 150-180 ℃ for a positive vulcanization time.
The preparation method can be used for preparing the reprocessable silicate particle crosslinked epoxy rubber material, namely the particle reinforced reprocessable rubber material.
According to the invention, metal chloride is directly added into the epoxy rubber material filled with silicate particles to catalyze the reaction of rubber epoxy groups and silanol groups on the surfaces of the silicate particles to generate interface silicon ether bonds, and the silicate particles serve as a crosslinking center and a reinforcement to prepare the silicate particle crosslinked epoxy rubber material with high mechanical property. Meanwhile, the topological structure of the rubber cross-linked network is rearranged by utilizing the alkoxy exchange reaction among the silicon ether cross-linked bonds at high temperature, so that the rubber material can be repeatedly processed and recycled, and the method has important significance for environmental protection and social sustainable development.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, metal chloride with Lewis acidity is added into epoxy rubber filled with silicate particles to directly catalyze the formation of silicon ether bonds at rubber/particle interfaces, so as to prepare a silicate particle crosslinked rubber material; meanwhile, the metal chloride catalyzes the alkoxy exchange reaction among the interface silicon ether groups to realize the repeatable processing of the cross-linked rubber, and the processed rubber material has high performance retention rate and can be repeatedly processed;
(2) the main raw materials adopted by the invention adopt industrial general raw materials, so that the cost is low; the vulcanization crosslinking of the rubber material does not need to add additional accelerator and vulcanizing agent, and no by-product and toxic and harmful substances are generated; meanwhile, the whole processing and reprocessing process only needs to use conventional rubber processing equipment, and the process is simple; the invention has important prospect in preparing high-strength rubber materials capable of being repeatedly processed.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
(1) Sequentially adding epoxidized natural rubber, white carbon black and aluminum chloride into an internal mixer for mixing for 10 minutes at the mixing temperature of 80 ℃ to obtain mixed rubber;
(2) vulcanizing the obtained rubber compound at 180 ℃ according to positive vulcanization time;
(3) and (3) crushing the vulcanized rubber into 80-mesh rubber powder, and carrying out hot pressing at 180 ℃ for 20 minutes to obtain the reprocessed rubber.
By changing the adding amounts of white carbon black and aluminum chloride, a comparative sample and 5 examples were prepared according to the method of the present invention. The formulations of the comparative examples and examples are shown in Table 1 below, where the amounts of the substances are given in g.
TABLE 1
The properties of all the formulations of example 1 were fully tested according to the Chinese national standard GB/T528-2009, and the typical properties of the vulcanized rubber sample and the change of the properties after reprocessing are shown in Table 2 below. The test results show that the tensile strength and crosslinking density of the vulcanized rubber are improved along with the increase of the addition amount of the aluminum chloride. This is because the lewis acidity of aluminum chloride can catalyze the ring opening of epoxy groups in the rubber matrix and the addition reaction between the epoxy groups and silanol groups on the surface of white carbon black. The performance retention rate of the rubber subjected to repeated processing is more than 90% (the performance retention rate is the performance ratio of the sample after repeated processing to the original sample); the sample without aluminum chloride had a low crosslink density and could not be reprocessed and the properties could not be determined.
TABLE 2
Example 2
(1) Adding epoxidized styrene butadiene rubber, montmorillonite and zinc chloride into an internal mixer in sequence, and mixing for 10 minutes at the mixing temperature of 50 ℃ to obtain rubber compound;
(2) vulcanizing the obtained rubber compound at 150 ℃ according to positive vulcanization time;
(3) and (3) crushing the vulcanized rubber into 80-mesh rubber powder, and carrying out hot pressing at 150 ℃ for 60 minutes to obtain the reprocessed rubber.
A control and 4 examples were prepared according to the above method of the present invention, varying the amounts of montmorillonite and aluminum chloride added. The comparative and example formulations are shown in Table 3 below, where the amounts of the materials are given in grams.
TABLE 3
The properties were tested according to the Chinese national standard GB/T528-2009, and the typical properties of the vulcanizate samples and the property changes after reprocessing are shown in Table 4 below. The test result shows that the stretching strength and the crosslinking density of the vulcanized rubber can be obviously improved along with the increase of the addition of the zinc chloride, because the Lewis acidity of the zinc chloride can catalyze the ring opening of an epoxy group in a rubber matrix and the addition reaction between the epoxy group and silanol groups on the surface of the montmorillonite. With the increase of the addition of montmorillonite and zinc chloride, the tensile strength, the stretching strength and the crosslinking density of the vulcanized rubber are gradually increased. The performance retention rate of the rubber subjected to repeated processing is more than 90% (the performance retention rate is the performance ratio of the sample after repeated processing to the original sample); the control sample without zinc chloride had a low crosslink density and could not be reprocessed and the properties could not be determined.
TABLE 4
Embodiment 3
(1) Sequentially adding epoxidized butadiene rubber, kaolin and ferric chloride into an internal mixer for mixing for 10 minutes at the mixing temperature of 30 ℃ to obtain rubber compound;
(2) vulcanizing the obtained rubber compound at 160 ℃ according to positive vulcanization time;
(3) and crushing the vulcanized rubber into 80-mesh rubber powder, and carrying out hot pressing at 160 ℃ for 30 minutes to obtain the reprocessed rubber.
A control and 4 examples were prepared according to the invention as described above, varying the amounts of kaolin and aluminum chloride added. The comparative and example formulations are given in Table 5 below, wherein the amounts of the substances are given in g.
TABLE 5
The properties were tested according to the Chinese national standard GB/T528-2009, and the typical properties of the vulcanizate samples and the property changes after reprocessing are shown in Table 6 below. The test result shows that the crosslinking density and the stretching strength of the vulcanized rubber are obviously improved along with the addition of the ferric chloride, and the iron chloride catalyzes the ring opening of an epoxy group in an epoxidized butadiene rubber molecular chain and performs an addition reaction with a silanol group on the surface of the kaolin due to the Lewis acid performance of the ferric chloride. The addition amounts of kaolin and ferric chloride are increased, and the tensile strength, the stretching strength and the crosslinking density of the vulcanized rubber are gradually improved. The performance retention rate of the rubber subjected to repeated processing is more than 90% (the performance retention rate is the performance ratio of the sample after repeated processing to the original sample); the control without ferric chloride had a low crosslink density and could not be reprocessed and the properties could not be determined.
TABLE 6
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. A method of preparing a particulate reinforced reprocessable rubber material, comprising the steps of:
(1) sequentially adding epoxy rubber, silicate filler and catalyst into an open mill or an internal mixer for blending to obtain rubber compound; the catalyst is more than one of aluminum chloride, magnesium chloride, ferric chloride, zinc chloride, stannic chloride, stannous chloride and niobium pentachloride;
(2) and adding an anti-aging agent into the rubber compound at room temperature, and carrying out hot-pressing crosslinking to obtain the particle-reinforced rubber material capable of being repeatedly processed.
2. The method of claim 1, wherein the repeated processing comprises the steps of crushing the vulcanized rubber into rubber powder having a particle size of 80 mesh, and then hot-pressing the rubber powder into rubber; the hot-pressing temperature of the rubber powder is 150-180 DEG CºAnd C, hot pressing for 20-60 minutes.
3. The method as claimed in claim 1, wherein in step (1), the gel content of the mix is 65.5-90.5 wt.%, the filler content of the mix is 9-33 wt.%, and the catalyst content of the mix is 0.5-1.5 wt.%.
4. The method according to claim 1, wherein in the step (1), the epoxy rubber is one or more of epoxidized butadiene rubber, epoxidized natural rubber, epoxidized styrene-butadiene rubber, epoxidized nitrile rubber and epoxidized ethylene-propylene rubber; the epoxy degree of the epoxy rubber is 20-50%.
5. The method according to claim 1, wherein in step (1), the silicate filler is one or more of silica, montmorillonite, kaolin, vermiculite, rectorite, sepiolite, attapulgite, imogolite, mica, and halloysite.
6. The method of claim 1, wherein in step (1), the blending temperature is 30-80%ºC; the blending time is 10-20 minutes.
7. The method according to claim 1, wherein in the step (2), the antioxidant is N-isopropyl-N ' -phenyl-p-phenylenediamine, N-cyclohexyl-N ' -phenyl-p-phenylenediamine, N- (1, 3-dimethyl) butyl-N ' -phenyl-p-phenylenediamine, N-diphenyl-p-phenylenediamine, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2 ' -methylenebis (4-methyl-6-tert-butylphenol), 2,4, 6-tri-tert-butylphenol, 4' -thiobis (6-tert-butyl-3-methylphenol), 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline and 9, 9-dimethylacridine; the dosage of the anti-aging agent is 1.5-4 wt% of the mass of the epoxy rubber.
8. The method as claimed in claim 1, wherein the step (2) of hot-pressing crosslinking is performed at 150-ºAnd C, performing mould pressing according to the positive vulcanization time.
9. A particulate reinforced reprocessable rubber material produced by the production process as claimed in any one of claims 1 to 8.
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| CN111944093B (en) * | 2020-08-20 | 2022-06-17 | 宁波大学 | Elastomer capable of being repeatedly processed and preparation method thereof |
| CN111995802B (en) * | 2020-09-07 | 2021-09-10 | 华东理工大学 | Raw material composition, rubber material, and preparation method and application thereof |
| CN113024917B (en) * | 2021-04-09 | 2022-03-25 | 华南理工大学 | Method for preparing rubber capable of being repeatedly processed based on dithioacetal exchange reaction |
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| CN1572825A (en) * | 2003-06-03 | 2005-02-02 | 住友橡胶工业株式会社 | Rubber composition for tread and pneumatic tyre using the same |
| CN103282418A (en) * | 2010-12-29 | 2013-09-04 | 朗盛德国有限责任公司 | Vulcanizable compositions based on nitrile rubbers containing epoxy groups |
| CN104788868A (en) * | 2015-04-24 | 2015-07-22 | 福建师范大学泉港石化研究院 | Method for preparing rubber from metal salt containing concentration water through coordination crosslinking |
| CN106589776A (en) * | 2016-12-16 | 2017-04-26 | 安徽亚兰密封件有限公司 | High-toughness recoverable rubber sealing piece |
| CN108641150A (en) * | 2018-04-08 | 2018-10-12 | 华南理工大学 | A kind of repeatable processing rubber material and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1572825A (en) * | 2003-06-03 | 2005-02-02 | 住友橡胶工业株式会社 | Rubber composition for tread and pneumatic tyre using the same |
| CN103282418A (en) * | 2010-12-29 | 2013-09-04 | 朗盛德国有限责任公司 | Vulcanizable compositions based on nitrile rubbers containing epoxy groups |
| CN104788868A (en) * | 2015-04-24 | 2015-07-22 | 福建师范大学泉港石化研究院 | Method for preparing rubber from metal salt containing concentration water through coordination crosslinking |
| CN106589776A (en) * | 2016-12-16 | 2017-04-26 | 安徽亚兰密封件有限公司 | High-toughness recoverable rubber sealing piece |
| CN108641150A (en) * | 2018-04-08 | 2018-10-12 | 华南理工大学 | A kind of repeatable processing rubber material and preparation method thereof |
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